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1.
Resonance-enhanced multiphoton ionization (REMPI) of the \(\tilde B\) and \(\tilde C'\) states of NH3 in a pulsed supersonic molecular beam was observed at 304–340 nm, using the multiphoton-ionization mass-spectrometer system described herein. The observed features are the result of a 2+1 MPI process and correspond quite well with the reported 3+1 MPI of NH3 in the literature from the ground state of opposite parity. 相似文献
2.
P. J. Ziemann A. W. Castleman Jr. 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,20(1):97-99
Gas phase (MgO) n + and (MgO) n Mg+ clusters were produced in a gas aggregation source and studied by using laser-ionization time-of-flight mass spectrometry. A MgO molecule apparently serves as the nucleus for cluster growth, to which Mg and O atoms add. The heat generated by the formation of metal-oxygen bonds, and that added to the cluster by ionization leads to the production of clusters with the stoichiometry of the stable high-temperature oxide. The abundance maxima observed in the mass spectra indicate that the clusters form compact cubic structures similar to pieces of the MgO crystal lattice. The primary fragmentation channel responsible for the observed patterns is probably the loss of MgO monomers. 相似文献
3.
In this work, we report experimental results from the strong-field ionization and subsequent Coulomb explosion of narrow distributions of small (<40 atoms) heteronuclear clusters composed of transition metal (Ti, V, Cr, Nb, or Ta) and carbon atoms. Analysis of the resulting multiply charged ions was performed through time-of-flight mass spectrometry, and evidence regarding ionization dynamics was obtained. The data reveal the presence of enhanced ionization during exposure to the ultrashort (~100 fs) pulse resulting in the formation of ions possessing significantly higher charge states than those predicted from atomic species. Regardless of the transition metal species, we observe the absorption of similar amounts of energy from the external field, as indicated by the maximum observed charge states in each experiment. These results are compared to our previously reported study on the strong-field ionization of transition metal oxide clusters. We observe identical maximum observable charge states for each of the transition metal species resulting from both metal oxide and metal carbide clusters. 相似文献
4.
We investigated the halogenation reactivity of copper cluster anions produced via a magnetron-sputter source after introduction into a fast-flow tube reaction apparatus simultaneously with chlorine gas. Interesting cluster products corresponding to [Cu(n)Cl(n+1)](-) (n = 1-6) were observed with notable stability, and the mass distribution of these clusters exhibits an exponential decay with increasing values of n. Reaction kinetics analysis is provided on the gas-phase reactivity of copper cluster anions with chlorine. First-principle calculations suggest a series of cubic-like structures for these species similar to the structure of alkali halide clusters due to their similar electronic configurations. These structures act as a starting point in the formation of ionic crystals. 相似文献
5.
Clayborne PA Gupta U Reber AC Melko JJ Khanna SN Castleman AW 《The Journal of chemical physics》2010,133(13):134302
Three-dimensional aromaticity is shown to play a role in the stability of deltahedral Zintl clusters and here we examine the connection between aromaticity and stability. In order to gain further insight, we have studied Zintl analogs comprised of bismuth doped tin clusters with photoelectron spectroscopy and theoretical methods. To assign aromaticity, we examine the ring currents induced around the cage by using the nucleus independent chemical shift. In the current study, BiSn(4)(-) is a stable cluster and fits aromatic criteria, while BiSn(5)(-) is found to fit antiaromatic criteria and has reduced stability. The more stable clusters exhibit an aromatic character which originates from weakly interacting s-states and bonding orbitals parallel to the surface of the cluster, while nonbonding lone pairs perpendicular to the surface of the cluster account for antiaromaticity and reduced stability. The effect of three-dimensional aromaticity on the electronic structure does not result in degeneracies, so the resulting variations in stability are smaller than those seen in conventional aromaticity. 相似文献
6.
Dermota TE Hydutsky DP Bianco NJ Castleman AW 《The journal of physical chemistry. A》2005,109(37):8259-8267
A study of the excited-state dynamics of (SO2)m clusters following excitation by ultrafast laser pulses in the range of 4.5 eV (coupled 1A2, 1B1 states) and 9 eV (F band) is presented. The findings for the coupled 1A2 and 1B1 states are in good agreement with published computational work on the properties of these coupled states. A mechanism involving charge transfer to solvent is put forward as the source of the excited-state dynamics that follow the excitation of the SO2 F band within (SO2)m+1 clusters with m > 1. The proposed CTTS mechanism is supported by calculations of the energetics of the process and the observed trends in the excited-state lifetimes that correlate very well with the calculated energies. 相似文献
7.
Justes DR Mitrić R Moore NA Bonacić-Koutecký V Castleman AW 《Journal of the American Chemical Society》2003,125(20):6289-6299
We present joint theoretical and experimental results which provide evidence for the selectivity of V(x)O(y)(+) clusters in reactions toward ethylene due to the charge and different oxidation states of vanadium for different cluster sizes. Density functional calculations were performed on the reactions between V(x)O(y)(+) and ethylene, allowing us to identify the structure-reactivity relationship and to corroborate the experimental results obtained by Castleman and co-workers (Zemski, K. A.; Justes, D. R.; Castleman, A. W., Jr. J. Phys. Chem. A 2001, 105, 10237). The lowest-energy structures for the V(2)O(2)(-)(6)(+) and V(4)O(8)(-)(10)(+) clusters and the V(2)O(3)(-)(6)(+)-C(2)H(4) and V(4)O(10)(+)-C(2)H(4) complexes, as well as the energetics for reactions between ethylene and V(2)O(4)(-)(6)(+) and V(4)O(10)(+) are presented here. The oxygen transfer reaction pathway was determined to be the most energetically favorable one available to V(2)O(5)(+) and V(4)O(10)(+) via a radical-cation mechanism.The association and replacement reaction pathways were found to be the optimal channels for V(2)O(4)(+) and V(2)O(6)(+), respectively. These results are in agreement with the experimental results reported previously. Experiments were also conducted for the reactions between V(2)O(5)(+) and ethylene to include an energetic analysis at increasing pressures. It was found that the addition of energy depleted the production of V(2)O(4)(+), confirming that a more involved reaction rather than a collisional process is responsible for the observed phenomenon. In this contribution we show that investigation of reactions involving gas-phase cationic vanadium oxide clusters with small hydrocarbons is suitable for the identification of reactive centers responsible for selectivity in heterogeneous catalysis. 相似文献
8.
Goken EG Joshi KL Russo MF van Duin AC Castleman AW 《The journal of physical chemistry. A》2011,115(18):4657-4664
Computational chemistry simulations were performed to determine the effect that the addition of a single formic acid molecule has on the structure and stability of protonated water clusters. Previous experimental studies showed that addition of formic acid to protonated pure water results in higher intensities of large-sized clusters when compared to pure water and methanol-water mixed clusters. For larger, protonated clusters, molecular dynamics simulations were performed on H(+)(H(2)O)(n), H(+)(H(2)O)(n)CH(3)OH, and H(+)(H(2)O)(n)CHOOH clusters, 19-28 molecules in size, using a reactive force field (ReaxFF). Based on these computations, formic acid-water clusters were found to have significantly higher binding energies per molecule. Addition of formic acid to a water cluster was found to alter the structure of the hydrogen-bonding network, creating selective sites within the cluster, enabling the formation of new hydrogen bonds, and increasing both the stability of the cluster and its rate of growth. 相似文献
9.
Reber AC Khanna SN Tyo EC Harmon CL Castleman AW 《The Journal of chemical physics》2011,135(23):234303
Cooperative reactivity plays an important role in the oxidation of CO to CO(2) by palladium oxide cations and offers insight into factors which influence catalysis. Comprehensive studies including guided-ion-beam mass spectrometry and theoretical investigations reveal the reaction products and profiles of PdO(2)(+) and PdO(3)(+) with CO through oxygen radical centers and dioxygen complexes bound to the Pd atom. O radical centers are more reactive than the dioxygen complexes, and experimental evidence of both direct and cooperative CO oxidation with the adsorption of two CO molecules are observed. The binding of multiple electron withdrawing CO molecules is found to increase the barrier heights for reactivity due to decreased binding of the secondary CO molecule, however, reactivity is enhanced by the increase in kinetic energy available to hurdle the barrier. We examine the effect of oxygen sites, cooperative ligands, and spin including two-state reactivity. 相似文献
10.
Z. Y. Chen B. D. May A. W. Castleman Jr. 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1993,25(3):239-246
The potential energy surface (PES) of linear Ar 3 + is calculated at the MP4/6-31G* level including all single, double, triple and quadruple excitations. The results show that the PES of the linear Ar 3 + has a very flat valley along the asymmetric stretching vibration normal mode, ν3. A higher level quadratic configuration interaction calculation including single, double and triple substitutions QCISD (T) along this flat valley suggests that an asymmetric geometry energy minimum reported earlier based on MP2 [1] is due to symmetry breaking in UHF. The global minimum of the PES is found to be for the symmetric geometry atR ab =R bc =2.66±0.01 Å, which is in good agreement with the MRD-CI calculation [2] and expectations from our earlier photodissociation experiments [3]. The calculational results are compared with other theoretical calculations, and are discussed in the context of the photodissociation and dynamics of dissociation experiments conducted on Ar 3 + . 相似文献